N,N&#39;-bridged-bis[2-alkyl-2-hydroxyethylamines]

ABSTRACT

N,N&#39;-Bridged-bis[(O and/or N-substituted)-2-alkyl-2-hydroxyethylamines] of the formula ##STR1## are prepared by condensing an epoxide of the formula ##STR2## and a diamine of the formula R&#39;NH-X-NHR&#39;. The products and dicarbanilates, acid-addition salts, N,N&#39;-dioxides and N,N&#39;-diammonium quaternary salts derived therefrom have antibacterial activity in vitro and are useful as antibacterial agents.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a division of our application Ser. No. 332,267,filed Feb. 14, 1973, now Pat. No. 3,928,427 which is acontinuation-in-part of our application Ser. No. 123,097, filed Mar. 10,1971 and now abandoned.

FIELD OF THE INVENTION

This invention relates to compositions of matter classified in the artof organic chemistry as N,N'-bridged-bis-[(0 and/orN-substituted)-2-alkyl-2-hydroxyethylamines] and to a process forpreparing them.

SUMMARY OF THE INVENTION

In its composition of matter aspect our invention providesN,N'-(X)-bis[N-(R')-2-(R)-2-(ZO)-ethylamine] of the formula ##STR3##wherein: R is alkyl of three to fifteen carbon atoms or cycloalkyl offour to seven ring carbon atoms;

R' is hydrogen or atertiary alkyl of one to four carbon atoms;

X is alkylene of two to twelve carbon atoms with bonds to the nitrogenatoms at different carbon atoms or X'-Y-X", wherein X' and X" arealkylene of one to four carbon atoms with bonds to Y and to the nitrogenatoms at the same or different carbon atoms and Y is cycloalkylene offour to seven ring carbon atoms with bonds to X' and X" at the same ordifferent carbon atoms, phenylene, vinylene or ethynylene;

The sum of the number of carbon atoms of R and X is at least nine;

Z is hydrogen or, when R' is atertiary alkyl of one to four carbonatoms, N-phenylcarbamoyl or N-phenylcarbamoyl substituted in the benzenering by one to three members selected from the group consisting ofatertiary alkyl of one to four carbon atoms, halo and atertiary alkoxyof one to four carbon atoms or by a member selected from the groupconsisting of trifluoromethyl, acetamido, nitro, and methylsulphonyl;

Acid-addition salts thereof; and,

When R' is atertiary alkyl of one to four carbon atoms and Z ishydrogen, N,N'-dioxides, N,N'-di(atertiary alkyl of one to four carbonatoms)diammonium quaternary salts and N,N'-dibenzyldiammonium quaternarysalts thereof.

The compounds of Formula I and acid-addition salts,

N,n'-dioxides and N,N'-diammonium quaternary salts thereof haveantibacterial activity in vitro and are useful as antibacterial agents.

In its process aspect our invention provides the process for preparingN,N'-(X)-bis[N-(R')-2-(R)-2-(ZO)-ethylamine] of Formula I, wherein Z ishydrogen, which comprises condensing an epoxide of the formula ##STR4##with a diamine of the formula ##STR5##

    R'NH-X-NHR'                                                (Formula III),

wherein R of Formula II and R' and X of Formula III have the samemeanings ascribed thereto in Formula I.

DETAILED DESCRIPTION OF THE INVENTION

When R is alkyl of three to fifteen carbon atoms, it is normal alkyl orbranched alkyl as illustrated by propyl, isopropyl, butyl, isobutyl,sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl,undecyl, dodecyl, tridecyl, tetradecyl and pentadecyl. Since R and ethylare integral, The solvents -hydroxyheptyl] R= X= Y= they are namedintegrally when R is alkyl. Thus, the illustrated alkyls becomerespectively, pentyl, 3-methylbutyl, hexyl, 4-methylpentyl,2-methylpentyl, 3,3-dimethylbutyl, heptyl, octyl, nonyl, decyl, undecyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl and heptadecyl.

When R is cycloalkyl of four to seven ring carbon atoms, it iscyclobutyl, cyclopentyl, cyclohexyl or cycloheptyl.

When R' is atertiary alkyl of one to four carbon atoms, it is methyl,ethyl, propyl, isopropyl, butyl, isobutyl or sec-butyl.

When X is alkylene of two to twelve carbon atoms with bonds to thenitrogen atoms at different carbon atoms, it can be unbranched orbranched. If unbranched, X is 1.2-ethylene, 1,3-propylene, 1,4-butylene,1,5-pentylene, 1,6-hexylene, 1,7-heptylene, 1,8-octylene, 1,9-nonylene,1,10-decylene, 1,11-undecylene or 1,12-dodecylene. If branched, X is,for example, 1,2-propylene, 2,4-butylene, 2,10-dodecylene, or2-methyl-1,4-butylene.

When X is X'-Y-X", X' and X" can be the same or different and can beunbranched or branched alkylene of one to four carbon atoms with bondsto Y and to the nitrogen atoms at the same or different carbon atoms asillustrated by methylene, ethylene, ethylidene or 1,4-butylene. When Yis cycloalkylene of four to seven ring carbon atoms with bonds to X' andX" at the same or different carbon atoms, it is, for example,cyclobutylidene, 1,4-cyclohexylene or 1,2-cycloheptylene. When Y iscycloalkylene or vinylene, the bonds to X' and X" can be cis or trans.Thus, X'-Y-X" is, for example, 1,3-cyclobutylenebismethyl,1,4-cyclohexylenebismethyl, cis-1,4-cyclohexylenebismethyl,trans-1,4-cyclohexylenebismethyl, 1,2-cycloheptylenebismethyl,cyclohexylene-1-methyl-4-(2-ethyl), cyclohexylene-1-methyl-4-(1-ethyl),cyclohexylene-1-methyl-4-(4-butyl), 1,4-phenylenebismethyl,trans-1,4-(2-butenylene) and 1,4-(2-butynylene).

when Z is N-phenylcarbamoyl substituted in the benzene ring, it is, forexample, N-(o-tolyl)carbamoyl, N-(p-bromophenyl)carbamoyl,N-(m-methoxyphenyl)carbamoyl, N-(4-chloro-o-tolyl)carbamoyl,N-(5-chloro-2,4-dimethoxyphenyl)carbamoyl,N-[m-(trifluoromethyl)phenyl]carbamoyl, N-(p-acetamidophenyl)carbamoyl,N-(m-nitrophenyl)carbamoyl, or N-[p-(methylsulfonyl)phenyl]carbamoyl.Named as substituted carbanilates the illustrated substitutedN-phenylcarbamoyls are, respectively, o-methylcarbanilate,p-bromocarbanilate, m-methoxycarbanilate, 2-methyl-4-chlorocarbanilate,5-chloro-2,4-dimethoxycarbanilate, m-(trifluoromethyl)carbanilate,p-acetamidocarbanilate, m-nitrocarbanilate andp-(methylsulfonyl)carbanilate. When N-phenylcarbamoyl is substituted inthe benzene ring by halo, halo is fluoro, chloro, bromo or iodo.

In N,N'-diammonium quaternary salts of the compounds of Formula Iwherein R' is alkyl, atertiary alkyl of one to four carbon atoms can bemethyl, ethyl, propyl, isopropyl, butyl, isobutyl or sec-butyl.

The manner and process of making and using the invention and the bestmode of carrying it out will now be described so as to enable any personskilled in the art to which it pertains to make and use it.

The preferred method for carrying out the process of condensing anepoxide of Formula II with a diamine of Formula III is the use ofsolvent inert under the reaction conditions, for example, acetonitrile,benzene, chloroform, N,N-dimethylformamide, ethanol, methanol ortetrahydrofuran at a temperature in the range of 0° to 100° C. Methanolis the preferred solvent and room temperature is the preferredtemperature.

Compounds of Formula I in which R' is methyl are also prepared bymethylating the corresponding compounds of Formula I in which R' ishydrogen with formaldehyde and formic acid.

Phenylcarbamoylation and phenylthiocarbamoylation of compounds ofFormula I wherein R' is alkyl and Z is hydrogen, formation ofacid-addition salts of the compounds of Formula I, and N,N'-dioxidationand N,N'-diquaternerization of the compounds of Formula I wherein R' isalkyl are all accomplished by standard methods.

The phenylisocyanates and phenylisothiocyanates required forphenylcarbamoylation and phenylthiocarbamoylation are known classes ofcompounds, some of which are commercially available. Those(substituted-phenyl)isocyanates which are not commercially available canbe prepared, for example, by passing carbonyl chloride into hotsolutions of the corresponding anilines in toluene, saturated withhydrogen chloride. Those (substituted-phenyl)isothiocyanates which arenot commercially available can be prepared, for example, by treating thecorresponding ammonium (substituted-phenyl) dithiocarbamates, preparedin turn from the corresponding substituted anilines, carbon disulfideand ammonia, with lead nitrate.

Acid-addition salts of the compounds of Formula I can be prepared withany pharmaceutically acceptable inorganic (mineral) or organic acid. Ifinorganic, the acid can be, for example, hydrochloric acid, hydrobromicacid, nitric acid, phosphoric acid or sulfamic acid. If organic, theacid can be, for example, acetic acid, glycolic acid, lactic acid,quinic acid, hydrocinnamic acid, succinic acid, tartaric acid, citricacid, methanesulfonic acid or benzenesulfonic acid.

N,N'-diammonium quaternary salts of compounds of Formula I wherein R' isalkyl can be prepared with any pharmaceutically acceptable atertiaryone-to-four-carbon alkyl or benzyl ester of a strong inorganic ororganic acid, for example, methyl chloride, methyl iodide, ethylp-toluenesulfonate, propyl bromide, isobutyl iodide or benzyl bromide.

That the acid and the alkyl ester be pharmaceutically acceptable meansthat the beneficial properties inherent in the free base not be vitiatedby side effects ascribable to the anions.

Although pharmaceutically acceptable salts are preferred, all salts arewithin the scope of the invention. A pharmaceutically unacceptable saltmay be useful, for example, for purposes of identification orpurification or in preparing a pharmaceutically acceptable salt byion-exchange procedures.

The intermediate epoxides of Formula II are a known class of compounds.Their preparation is accomplished by epoxidation of the corresponding1-alkenes and vinylcycloalkanes by any of several well-known methods,for example, by the use of peracetic acid buffered with sodium acetate.The 1-alkenes and vinylcycloalkanes are known compounds, some of whichare commercially available.

The intermediate diamines of Formula III are also a known class ofcompounds, some of which are commercially available. Preparation ofthose which are not commercially available is accomplished by well-knownmethods, for example, by reductive amination of the correspondingdiketone or dialdehyde, amination of the corresponding dihalide ordialcohol p-toluenesulfonate diester or reduction of the correspondingdinitrile, dioxime, diamide, diazide or other di-higher-oxidation-statenitrogen compound. Unsymmetrical diamines can be prepared fromunsymmetrical starting materials.

The compounds of Formula I and acid-addition salts, N,N'-dioxides andN,N'-diammonium quaternary salts thereof are purified by distillation orby recrystallization. Their structures follow from their route ofsynthesis and are corroborated by infrared spectral analysis and by thecorrespondence of calculated and found values of elemental analysis ofrepresentative samples.

As stated above the compounds of Formula I and acid-addition salts,N,N'-dioxides and N,N'-diammonium quaternary salts thereof haveantibacterial activity in vitro, which was determined by a standardserial dilution test. In this test the concentration of compoundarresting the growth of the microorganism is the bacteriostaticconcentration and is expressed in parts per million (p.p.m.). Theconcentration of compound preventing growth of the microorganism afterfurther incubation is the bactericidal concentration and is alsoexpressed in parts per million.

The compounds of Formula I and acid-addition salts, N,N'-dioxides andN,N'-diammonium quaternary salts thereof are useful as antibacterialagents and are especially useful for disinfecting and sanitizing livingand non-living surfaces by conventional swabbing, padding, spraying,immersing, rinsing and the like techniques. Depending on the particularpurpose involved, the compounds are used in aqueous solution, in aqueousdetergent solutions or in solutions in organic solvents.

The following examples illustrate specific embodiments of our inventionwithout limiting the latter thereto.

EXAMPLE 1

A solution of 1-undecene oxide (88.8 g.), hexamethylenediamine(1,6-hexanediamine, 30.3 g.) and methanol (400 ml.) was allowed to standat 0° C. overnight, then at room temperature over the weekend. The solidwas collected and recrystallized from ethanol, affordingN,N'-(1,6-hexylene)-bis[2-hydroxyundecylamine] (I: R= CH₃ (CH₂)₈, R' =X= (CH₂)₆ ; Z= H)(m.p. 122.6°-129.0° C.).

Hydrogen bromide was bubbled through a solution ofN,N'-(1,6-hexylene)-bis[2-hydroxyundecylamine] (5 g.) in methanol (100ml.). The resulting solid was collected (4.6 g.) and recrystallized frommethanol, affording N,N'-(1,6-hexylene)-bis[2-hydroxyundecylamine]dihydrobromide (2.4 g., m.p. 299°-301° C.).

A solution of N,N'-(1,6-hexylene-bis[2-hydroxyundecylamine] (5 g.),glycolic acid (1.66 g.) and methanol was heated until the solidsdissolved, then evaporated to dryness. Recrystallization of the solidfrom acetone afforded N,N'-(1,6-hexylene)-bis[2-hydroxyundecylamine]diglycolate (4.6 g., m.p. 88.2°-94.6° C.). In a similar manner usingacetic acid and lactic acid instead of glycolic acid there wereobtained, respectively, N,N'-(1,6-hexylene)-bis[2-hydroxyundecylamine]diacetate (m.p. 113°-120.6° C.) andN,N'-(1,6-hexylene)-bis[2-hydroxyundecylamine] dilactate (m.p.102.0°-104.0° C.).

Using hydrochloric acid, nitric acid, phosphoric acid, sulfamic acid,quinic acid, hydrocinnamic acid, succinic acid, tartaric acid, citricacid, methanesulfonic acid and benzenesulfonic acid, there are obtained,respectively:

N,n'-(1,6-hexylene)-bis[2-hydroxyundecylamine] dihydrochloride;

N,n'-(1,6-hexylene)-bis[2-hydroxyundecylamine] dinitrate;

N,n'-(1,6-hexylene)-bis[2-hydroxyundecylamine] diphosphate;

N,n'-(1,6-hexylene)-bis[2-hydroxyundecylamine] disulfamate;

N,n'-(1,6-hexylene)-bis[2-hydroxyundecylamine] diquinate;

N,n'-(1,6-hexylene)-bis[2-hydroxyundecylamine] dihydrocinnamate;

N,n'-(1,6-hexylene)-bis[2-hydroxyundecylamine] succinate;

N,n'-(1,6-hexylene)-bis[2-hydroxyundecylamine] tartrate;

N,n'-(1,6-hexylene)-bis[2-hydroxyundecylamine] dicitrate;

N,n'-(1,6-hexylene)-bis[2-hydroxyundecylamine] dimethanesulfonate; andN,N'-(1,6-hexylene)-bis[2-hydroxyundecylamine] dibenzenesulfonate.

Table I shows the results of the antibacterial testing in vitro ofN,N'-(1,6-hexylene)-bis[2 -hydroxyundecylamine].

                  Table I                                                         ______________________________________                                                      Bacteriostatic con-                                                                         Bactericidal con-                                 Microorganism centration (p.p.m.)                                                                         centration (p.p.m.)                               ______________________________________                                        Staphylococcus aureus                                                                       2.5           5                                                 Eberthella typhi                                                                            5             5                                                 Clostridium welchii                                                                         10            10                                                Pseudomonas aeruginosa                                                                      7.5           25                                                ______________________________________                                    

EXAMPLE 2

Condensation of 1-pentene oxide and hexamethylenediamine affordsN,N'-(1,6-hexylene)-bis[2-hydroxypentylamine] (I: R= CH₃ (CH₂)₂, R' = H,X= (CH₂)₆, Z= H).

EXAMPLE 3

Condensation of 3-methyl-1-butene oxide and hexamethylenediamine affordsN,N'-(1,6-hexylene)-bis[2-hydroxy-3-methylbutylamine] (I: R= (CH₃)₂ CH,R' = H, X= (CH₂)₆, Z= H).

EXAMPLE 4

Condensation of 1-hexene oxide and hexamethylenediamine affordsN,N'-(1,6-hexylene)-bis[2-hydroxyhexylamine] (I: R= CH₃ (CH₂)₃, R' = H,X= (CH₂)₆, Z= H).

EXAMPLE 5

Condensation of 4-methyl-1-pentene oxide and hexamethylenediamineaffords N,N'-(1,6-hexylene)-bis[2-hydroxy-4-methylpentylamine] (I: R=(CH₃)₂ CHCH₂, R' = H, X= (CH₂)₆, Z= H).

EXAMPLE 6

Condensation of 3-methyl-1-pentene oxide and hexamethylenediamineaffords N,N'-(1,6-hexylene)-bis[2-hydroxy-3-methylpentylamine] (I: R=CH₃ CH₂ (CH₃)C, R' = H, X= (CH₂)₆, Z= H).

EXAMPLE 7

Condensation of 3,3-dimethyl-1-butene oxide and hexamethylenediamineaffords N,N'-(1,6-hexylene)-bis[2-hydroxy-3,3-dimethylbutylamine] (I: R=(CH₃)₃ C, R' = H, X= (CH₂)₆, Z= H).

EXAMPLE 8

In a manner similar to that of Example 1, condensation of 1-hepteneoxide (71.8 g.) and hexamethylenediamine (32 g.) and recrystallizationof the resulting product from ethanol gaveN,N'-(1,6-hexylene)-bis[2-hydroxyheptylamine] (I: R= CH₃ (CH₂)₄, R' = H,X= (CH₂)₆, Z= H) (16.5 g., m.p. 131.2°-134.2° C.).

EXAMPLE 9

In a manner similar to that of Example 1, condensation of 1-octene oxide(42 g.) and hexamethylenediamine (19.05 g.) and recrystallization of theresulting product from methanol gaveN,N'-(1,6-hexylene)-bis[2-hydroxyoctylamine] (I: R= CH₃ (CH₂)₅, R' = H,X= (CH₂)₆, Z= H) (17.2 g., m.p. 124.0°-127.4° C.).

EXAMPLE 10

In a manner similar to that of Example 1, condensation of 1-nonene oxide(97.4 g.) and hexamethylenediamine (39.8 g.) and recrystallization ofthe resulting product (67g.) from ethanol affordedN,N'-(1,6-hexylene)-bis[2-hydroxynonylamine] (I: R= CH₃ (CH₂)₆, R' = H,X= (CH₂)₆, Z= H) (67 g., m.p. 122°-129.2° C.).

Treatment of N,N'-(1,6-hexylene)-bis[2-hydroxynonylamine] (4g.) withlactic acid (2.12 g.) in methanol and recrystallaization of theresulting salt from acetone gaveN,N'-(1,6-hexylene)-bis[2-hydroxynonylamine] dilactate (3,3 g., m.p.103.0°-104.6° C.).

EXAMPLE 11

In a manner similar to that of Example 1, condensation of 1-decene oxide(50 g.) and hexamethylenediamine (18.6 g.) and recrystallization of theresulting product from methanol gaveN,N'-(1,6-hexylene)-bis[2-hydroxydecylamine] (I: R= CH₃ (CH₂)₇, R' = H,X= (CH₂)₆, Z= H) (25.4 g., m.p. 118.0°-126.8° C.).

EXAMPLE 12

In a manner similar to that of Example 1, condensation of 1-dodeceneoxide (50 g.) and hexamethylenediamine (15.8 g.) and recrystallizationof the resulting product from ethanol gaveN,N'-(1,6-hexylene)-bis[2-hydroxydodecylamine] (I: R= CH₃ (CH₂)₉, R' =H, X= (CH₂)₆, Z= H) (35 g., m.p. 123.6°-128.0° C.).

EXAMPLE 13

Condensation of 1-tridecene oxide and hexamethylenediamine affordsN,N'-(1,6-hexylene)-bis[2-hydroxytridecylamine] (I: R= CH₃ (CH₂)₁₀, R' =H, X= (CH₂)₆, Z= H).

EXAMPLE 14

In a manner similar to that of Example 1, condensation of 1-tetradeceneoxide (91.8 g.) and hexamethylenediamine (25 g.) and recrystallizationof the resulting product (71 g., m.p. 118°-121° C.) from ethanol gaveN,N'-(1,6-hexylene)-bis[2-hydroxytetradecylamine] (I: R= CH₃ (CH₂)₁₁, R'= H, X== (CH₂)₆, Z= H) (55.3 g., m.p. 122°-126° C.).

EXAMPLE 15

In a manner similar to that of Example 1, condensation of 1-pentadeceneoxide (81.7 g.) and hexamethylenediamine (21 g.) and recrystallizationof the resulting product (74.3 g.) from isopropyl alcohol gaveN,N'-(1,6-hexylene)-bis[2-hydroxypentadecylamine] (I: R= CH₃ (CH₂)₁₂, R'= H, X = (CH₂)₆, Z= H) (m.p. 117.4°-124.0° C.).

EXAMPLE 16

Condensation of 1-hexadecene oxide and hexamethylenediamine affordsN,N'-(1,6-hexylene)-bis[2-hydroxyhexadecylamine] (I: R= CH₃ (CH₂)₁₃, R'= H, X= (CH₂)₆, Z= H).

EXAMPLE 17

Condensation of 1-heptadecene oxide and hexamethylenediamine affordsN,N'-(1,6-hexylene)-bis[2-hydroxypheptadecylamine] (I: R= CH₃ (CH₂)₁₄,R' = H, X= (CH₂)₆, Z= H).

EXAMPLE 18

Condensation of vinylcyclobutane oxide and hexamethylenediamine affordsN,N'-(1,6-hexylene)-bis[2-hydroxy-2-cyclobutylethylamine] ##STR6##

EXAMPLE 19

Condensation of vinylcyclopentane oxide and hexamethylenediamine affordsN,N'-(1,6-hexylene)-bis[2-hydroxy-2-cyclopentylethylamine] ##STR7##

EXAMPLE 20

Condensation of vinylcyclohexane oxide and hexamethylenediamine affordsN,N'-(1,6-hexylene)-bis[2-hydroxy-2-cyclohexylethylamine] ##STR8##

EXAMPLE 21

Condensation of vinylcycloheptane and hexamethylenediamine affordsN,N'-(1,6-hexylene)-bis[2-hydroxy-2-cycloheptylethylamine] ##STR9##

EXAMPLE 22

A. N,N'-(1,6-Hexylene)-bis[2-hydroxyundecylamine] (25.6 g.) was added inportions to a solution of formic acid (98%, 25 ml.) and formaldehyde(60%, 15 ml.) held at 70° C. When the addition was complete theresulting solution was refluxed (9 hr.), then basified with sodiumhydroxide solution (35%). The solid was collected and treated withmethanolic potassium hydroxide. The mixture was diluted with water andextracted with ether. Concentretion of the ether extract anddistillation of the residue under vacuum afforded an oil (16 g., b.p.208°-214° C./0.05 mm.). Hydrogen bromide was bubbled through an etherealsolution of the oil. The resulting solid was recrystallized frometherisopropyl alcohol, affordingN,N'-(1,6-hexylene)-bis[N-methyl-2-hydroxyundecylamine] dihydrobromide(I: R= CH₃ (CH₂)₈, R' = CH₃, X= (CH₂)₆, Z= H) (m.p. 186.4°-189.8° C.).

B. Condensation of 1-undecene oxide andN,N'-dimethylhexamethylenediamine and treatment of the resulting productwith hydrogen bromide also affordsN,N'-(1,6-hexylene)-bis[N-methyl-2-hydroxyundecylamine] dihydrobromide.

Table II shows the results of the in vitro antibacterial testing ofN,N'-(1,6-hexylene)-bis[N-methyl-2-hydroxyundecylamine] dihydrobromide.

                  Table II                                                        ______________________________________                                                      Bacteriostatic con-                                                                         Bactericidal con-                                 Microorganism centration (p.p.m.)                                                                         centration (p.p.m.)                               ______________________________________                                        Staphylococcus aureus                                                                       2.5           7.5                                               Eberthella typhi                                                                            5             5                                                 Clostridium welchii                                                                         5             5                                                 Pseudomonas aeruginosa                                                                      25            50                                                ______________________________________                                    

EXAMPLE 23

Condensation of 1-undecene oxide and N,N'-diethylhexamethylenediamineaffords N,N'-(1,6-hexylene)-bis[N-ethyl-2-hydroxyundecylamine] (I: R=CH₃ (CH₂)₈, R' = CH₃ CH₂, X= (CH₂)₆, Z= H).

EXAMPLE 24

Condensation of 1-undecene oxide and N,N'-dipropylhexamethylenediamineaffords N,N'-(1,6-hexylene)-bis[N-propyl-2-hydroxyundecylamine] (I: R=CH₃ (CH₂)₈, R'=CH₃ (CH₂)₂, X= (CH₂)₆, Z= H).

EXAMPLE 25

Condensation of 1-undecene oxide andN,N'-di(isopropyl)hexamethylenediamine affordsN,N'-(1,6-hexylene)-bis[N-isopropyl-2-hydroxyundecylamine] (I: R= CH₃(CH₂)₈, R' = (CH₃)₂ CH, X= (CH₂)₆, Z= H).

EXAMPLE 26

Condensation of 1-undecene oxide and N,N'-dibutylhexamethylenediamineaffords N,N'-(1,6-hexylene)-bis[N-butyl-2-hydroxyundecylamine] (I: R=CH₃ (CH₂)₈, R' = CH₃ (CH₂)₃, X= (CH₂)₆, Z= H).

EXAMPLE 27

Condensation of 1-undecene oxide andN,N'-di(isobutyl)hexamethylenediamine affordsN,N'-(1,6-hexylene)-bis[N-isobutyl-2-hydroxyundecylamine] (I: R= CH₃(CH₂)₈, R' = (CH₃)₂ CHCH₂, X= (CH₂)₆, Z= H).

EXAMPLE 28

Condensation of 1-undecene oxide andN,N'-di(secbutyl)hexamethylenediamine affordsN,N'-(1,6-hexylene)-bis[N-(sec-butyl)-2-hydroxyundecylamine] (I: R= CH₃(CH₂)₈, R' = CH₃ CH₂ (CH₃)CH, X= (CH₂)₆, Z= H).

EXAMPLE 29

In a manner similar to that of Example 22, methylation ofN,N'-(1,6-hexylene)-bis[2-hydroxyheptylamine] (35.7 g.) treatment of aportion (18.0 g.) of the resulting product (35.6 g.) with hydrogenbromide and recrystallization of the resulting salt from acetone gaveN,N'-(1,6-hexylene)-bis[N-methyl-2-hydroxyheptylamine] (I: R= CH₃(CH₂)₄, R' = CH₃, X= (CH₂)₆, Z= H) dihydrobromide (15.5 g., m.p.147.0°-149.0° C.).

EXAMPLE 30

In a manner similar to that of Example 22, methylation ofN,N'-(1,6-hexylene)-bis[2-hydroxyoctylamine] (35 g.) and treatment ofthe resulting product (b.p. 177°-182° C./1 mm.) with hydrogen bromidegave N,N'-(1,6-hexylene)-bis[N-methyl-2- hydroxyoctylamine] (I: R= CH₃(CH₂)₅, R' = CH₃, X= (CH₂)₆, Z= H) dihydrobromide (19.1 g., m.p.167.0°-158.8° C.).

EXAMPLE 31

In a manner similar to that of Example 22, methylation ofN,N'-(1,6-hexylene)-bis[2-hydroxynonylamine] (36 g.) and treatment ofthe resulting product (25 g., b.p. 172°-176° C./0.05 mm.) with hydrogenbromide gave N,N'-(1.6-hexylene)-bis[N-methyl-2-hydroxynonylamine] (I:R= CH₃ (CH₂)₆, R' = CH₃, X= (CH₂)₆, Z= H) dihydrobromide (26.3 g., m.p.176.0° -177.0° C.).

EXAMPLE 32

In a manner similar to that of Example 22, methylation ofN,N'-(1,6-hexylene)-bis[2-hydroxydecylamine] (36.7 g.), treatment of theresulting product (17.5 g., b.p. 204°-206° C./0.03 mm.) with hydrogenbromide and recrystallization of the resulting salt from isopropylalcohol gave N,N'-(1,6-hexylene)-bis[N-methyl-2-hydroxydecylamine] (I:R= CH₃ (CH₂)₇, R' = CH₃, X= (CH₂)₆, Z= H) dihydrobromide (8.4 g., m.p.186.0°-187.6° C.).

EXAMPLE 33

In a manner similar to that of Example 22, methylation ofN,N'-(1,6-hexylene)-bis[2-hydroxydodecylamine] (25 g.), treatment of theresulting product (b.p. 217°-228° C/0.02 mm.) with hydrogen bromide andrecrystallization of the resulting salt from isopropyl alcohol gaveN,N'-(1,6-hexylene)-bis[N-methyl-2-hydroxydodecylamine] (I: R= CH₃(CH₂)₉, R' = CH₃, X= (CH₂)₆, Z= H) dihydrobromide (9.6 g., m.p.197.0°-198.4° C.).

EXAMPLE 34

In a manner similar to that of Example 22, methylation ofN,N'-(1,6-hexylene)-bis[2-hydroxytetradecylamine] (30 g.) gaveN,N'-(1,6-hexylene)-bis[N-methyl-2-hydroxytetradecylamine] (I: R= CH₃(CH₂)₁₁, R' = CH₃, X= (CH₂)₆, Z= H) as a brown oil (28.2 g.).

EXAMPLE 35

In a manner similar to that of Example 1, condensation of 1-decene oxide(100 g.) and ethylenediamine (19.2 g.) and recrystallization of aportion (20 g.) of the resulting solid (45 g.) from ethanol gaveN,N'-ethylenebis[2-hydroxydecylamine] (I: R= CH₃ (CH₂)₇, R' = H, X=(CH₂)₂, Z= H) (13.6 g., m.p. 140.0°-145.8° C.).

EXAMPLE 36

In a manner similar to that of Example 1, condensation of 1-undeceneoxide (40 g.) and ethylenediamine (7.07 g.) and two recrystallizationsof the resulting solid (14.9 g.) from ethanol gaveN,N'-ethylenebis[2-hydroxyundecylamine] (I: R= CH₃ (CH₂)₈, R' = H, X=(CH₂)₂, Z= H) (12.4 g., m.p. 130.2°-137.8° C.).

EXAMPLE 37

In a manner similar to that of Example 1, condensation of 1-dodeceneoxide (100 g.) and ethylenediamine (16.3 g.) and recrystallization ofpart (20 g.) of the resulting product (55.3 g.) from methanol gaveN,N'-ethylenebis[2-hydroxydodecylamine] (I: R= CH₃ (CH₂)₉, R' = H, X=(CH₂)₂, Z= H) (13.4 g., m.p. 137.0°-142.0° C.).

EXAMPLE 38

In a manner similar to that of Example 22, methylation ofN,N'-ethylenebis[2-hydroxydecylamine] (15 g.) and treatment of theresulting product with hydrogen bromide gaveN,N'ethylene-bis[N-methyl-2-hydroxydecylamine] (I: R= CH₃ (CH₂)₇, R' =CH₃, X= (CH₂)₂, Z= H) dihydrobromide (4.0 g., m.p. 152.0°-164.0° C.).

EXAMPLE 39

In a manner similar to that of Example 22, methylation ofN,N'-ethylenebis[2-hydroxyundecylamine] (30 g.), treatment of theresulting product with hydrogen bromide and recrystallization of theresulting salt from isopropyl alcohol gaveN,N'-ethylenebis[N-methyl-2-hydroxyundecylamine] (I: R= CH₃ (CH₂)₈, R' =CH₃, X= (CH₂)₂, Z= H) dihydrobromide (12.8 g., m.p. 151.0°-162.0° C.).

EXAMPLE 40

In a manner similar to that of Example 22, methylation ofN,N'-ethylenebis[2-hydroxydodecylamine] (35 g.), treatment of theresulting product with hydrogen bromide and recrystallization of theresulting salt from isopropyl alcohol gaveN,N'-ethylenebis[N-methyl-2-hydroxydodecylamine] (I: R= CH₃ (CH₂)₉, R' =CH₃, X= (CH₂)₂, Z= H) dihydrobromide (4.6 g., m.p. 162.0° C.).

EXAMPLE 41

In a manner similar to that of Example 1, condensation of 1-nonene oxide(120 g.) and 1,3-propanediamine (31.2 g.) and two recrystallizations ofthe resulting product from methanol gaveN,N'-(1,3-propylene)-bis[2-hydroxynonylamine] (I: R= CH₃ (CH₂)₆, R' = H,X= (CH₂)₃, Z= H) (13.2 g., m.p. 107.0°-109.0° C.).

EXAMPLE 42

In a manner similar to that of Example 1, condensation of 1-decene oxide(58 g.) and 1,3-propanediamine (13.8 g.) and three recrystallizations ofthe resulting product from methanol gaveN,N'-(1,3-propylene)-bis[2-hydroxydecylamine] (I: R= CH₃ (CH₂)₇, R' = H,X= (CH₂)₃, Z= H) (8.5 g., m.p. 104.0°-107.6° C.).

EXAMPLE 43

In a manner similar to that of Example 1, condensation of 1-undeceneoxide (104.6 g.) and 1,3-propanediamine (22.7 g.) and tworecrystallizations of the resulting product from methanol gaveN,N'-(1,3-propylene)-bis[2-hydroxyundecylamine] (I: R= CH₃ (CH₂)₈, R' =H, X= (CH₂)₃, Z= H) (29.0 g., m.p. 94.0°-103.0° C.).

EXAMPLE 44

In a manner similar to that of Example 1, condensation of 1-dodeceneoxide (100 g.) and 1,3-propanediamine (20.1 g.) and threerecrystallizations of the resulting product from isopropyl alcohol gaveN,N'-(1,3-propylene)-bis[2-hydroxydodecylamine](I: R= CH₃ (CH₂)₉, R' =H, X= (CH₂)₃, Z= H) (11.9 g., 96.0°-106.0° C.).

EXAMPLE 45

In a manner similar to that of Example 22, methylation ofN,N'-(1,3-propylene)-bis[2-hydroxynonylamine] (14 g.), treatment of theresulting product with hydrogen bromide and two recrystallizations ofthe resulting salt from acetonitrile gaveN,N'-(1,3-propylene)-bis[N-methyl-2-hydroxynonylamine] (I: R= CH₃(CH₂)₆, R' = CH₃, X= (CH₂)₃, Z= H) dihydrobromide (9.1 g., m.p.175.0°-189.0° C.).

EXAMPLE 46

In a manner similar to that of Example 22, methylation ofN,N'-(1,3-propylene)-bis[2-hydroxydecylamine] (21.4 g.), treatment ofthe resulting product with hydrogen bromide and four recrystallizationsof the resulting salt from ethyl acetate-isopropyl alcohol gaveN,N'-(1,3-propylene)-bis[N-methyl-2-hydroxydecylamine] (I: R= CH₃(CH₂)₇, R'= CH₃, X= (CH₂)₃, Z= H) dihydrobromide (9.0 g., m.p.174°-184.0° C.).

EXAMPLE 47

In a manner similar to that of Example 22, methylation ofN,N'-(1,3-propylene)-bis[2-hydroxyundecylamine] (16 g.), treatment ofthe resulting product with hydrogen bromide and recrystallization of theresulting salt from acetone gaveN,N'-(1,3-propylene)-bis[N-methyl-2-hydroxyundecylamine] (I: R= CH₃(CH₂)₈, R' = CH₃, X= (CH₂)₃, Z= H) dihydrobromide (12.9 g., m.p.176.0°-189.0° C.).

EXAMPLE 48

Condensation of 1-undecene oxide and 1,4-butanediamine affordsN,N'-(1,4-butylene)-bis[2-hydroxyundecylamine] (I: R= CH₃ (CH₂)₈, R' =H, X= (CH₂)₄, Z= H).

EXAMPLE 49

Condensation of 1-undecene oxide and 1,5-pentanediamine affordsN,N'-(1,5-pentylene)-bis[2-hydroxyundecylamine] (I: R= CH₃ (CH₂)₈, R' =H, X= (CH₂)₅, Z= H).

EXAMPLE 50

Condensation of 1-heptene oxide and 1,7-heptanediamine affordsN,N'-(1,7-heptylene)-bis[2-hydroxyheptylamine] (I: R= CH₃ (CH₂)₄, R' =H, X= (CH₂)₇, Z= H).

EXAMPLE 51

In a manner similar to that of Example 1, condensation of 1-hepteneoxide (52 g.) and 1,8-octanediamine (32.8 g.) and two recrystallizationsof the resulting product from methanol gaveN,N'-(1,8-octylene)-bis[2-hydroxyheptylamine] (I: R= CH₃ (CH₂)₄, R' = H,X= (CH₂)₈, Z= H) (17.2 g., m.p. 128.0°-132.8° C.).

EXAMPLE 52

In a manner similar to that of Example 22, methylation ofN,N'-(1,8-octylene)-bis[2-hydroxyheptylamine] (16.9 g.), treatment ofthe resulting product with hydrogen bromide and two recrystallizationsof the resulting salt from isopropyl alcohol gaveN,N'-(1,8-octylene)-bis[N-methyl-2-hydroxyheptylamine] (I: R= CH₃(CH₂)₄, R' = CH₃, X= (CH₂)₈, Z= H) dihydrobromide (15.9 g., m.p.177.0°-190.0° C.).

EXAMPLE 53

Condensation of 1-hexene oxide and 1,9-nonanediamine affordsN,N'-(1.9-nonylene)-bis[2-hydroxyhexylamine] (I: R= CH₃ (CH₂)₃, R' = H,X= (CH₂)₉, Z= H).

EXAMPLE 54

In a manner similar to that of Example 1, condensation of 1-hexene oxide(34.8 g.) and 1,10-decanediamine (30 g.) and recrystallization of theresulting product from isopropyl alcohol gaveN,N'-(1,10-decylene)-bis[2-hydroxyhexylamine] (I: R= CH₃ (CH₂)₃ R' = H,X= (CH₂)₁₀, Z= H) (8.9 g., m.p. 127.0°-137.0° C.).

EXAMPLE 55

Condensation of 1-pentene oxide and 1,11-undecanediamine affordsN,N'-(1,11-undecylene)-bis[2-hydroxypentylamine] (I: R= CH₃ (CH₂)₂, R' =H, X= (CH₂)₁₁, Z= H).

EXAMPLE 56

Condensation of 1-pentene oxide and 1,12-dodecanediamine affordsN,N-(1,12-dodecylene)-bis[2-hydroxypentylamine] (I: R= CH₃ (CH₂)₂, R' =H, X= (CH₂)₁₂, Z= H).

EXAMPLE 57

Condensation of 1-undecene oxide and 1-methyl-1,2-ethanediamine affordsN,N'-(1,2-propylene)-bis[2-hydroxyundecylamine] (I: R= CH₃ (CH₂)₈, R'=H, X= CH(CH₃)CH₂, Z= H).

EXAMPLE 58

Condensation of 1-undecene oxide and 1,2-dimethyl-1,2-ethanediamineaffords N,N'-(2,4-butylene)-bis[2-hydroxyundecylamine] (I: R= CH₃(CH₂)₈, R' = H, X= CH(CH₃)CH(CH₃), Z= H).

EXAMPLE 59

Condensation of 1-pentene oxide and 1,10-dimethyl-1,10-decanediamineaffords N,N'-(2,10-dodecylene)-bis[2-hydroxypentylamine] (I: R= CH₃(CH₂)₂, R' = H, X= CH(CH₃)(CH₂)₈ CH(CH₃), Z= H).

EXAMPLE 60

Condensation of 1-undecene oxide and 2-methyl-1,4-butanediamine affordsN,N'-(2-methyl-1,4-butylene)-bis[2-hydroxyundecylamine] (I: R= CH₃(CH₂)₈, R' = H, X= CH₂ CH(CH₃)CH₂ CH₂, Z= H).

EXAMPLE 61

In a manner similar to that of Example 1, condensation of 1-octene oxide(50 g.) and 1,4-cyclohexylenebis(methylamine) (27.8 g.) andrecrystallization of the resulting product from acetone gaveN,N'-(1,4-cyclohexylenebismethyl)-bis[2-hydroxyoctylamine] (I: R= CH₃(CH₂)₅, R' = H, X= CH₂ CH(CH₂ CH₂)₂ CHCH₂, Z= H), (12 g., m.p.90.0°-96.2° C.).

EXAMPLE 62

In a manner similar to that of Example 1, condensation of 1-decene oxide(two runs, 50 g. each) and 1,4-cyclohexylenebis(methylamine) (22.8 g.each run) and two recrystallizations of the products from acetone gaveN,N'-(1,4-cyclohexylenebismethyl)-bis[2-hydroxydecylamine] (I: R= CH₃(CH₂)₇, R' = H, X= CH₂ CH(CH₂ CH₂)₂ CHCH₂, Z= H) (18.4 g., m.p.92.0°-98.8° C.).

EXAMPLE 63

In a manner similar to that of Example 1, condensation of 1-decene oxide(96.6 g.) and cis-1,4-cyclohexylenebis(methylamine) (44.2 g.) and tworecrystallizations of the resulting product from acetone gaveN,N'-(cis-1,4-cyclohexylenebismethyl)-bis[2-hydroxydecylamine] (I: R=CH₃ (CH₂)₇, R' = H, X= cis-CH₂ CH(CH₂ CH₂)₂ CHCH₂, Z= H) (13.5 g., m.p.72.6°-77.4° C.).

EXAMPLE 64

In a manner similar to that of Example 1, condensation of 1-decene oxide(98.9 g.) and trans-1,4-cyclohexylenebis(methylamine) (45.2 g.) andrecrystallization of the resulting product from acetone gaveN,N'-(trans-1,4-cyclohexylenebismethyl)-bis[2-hydroxydecylamine] (I: R=CH₃ (CH₂)₇, R'= H, X= trans-CH₂ CH(CH₂ CH₂)₂ CHCH₂, Z= H) (23.3 g., m.p.101.0°-102.8° C.).

EXAMPLE 65

In a manner similar to that of Example 22, methylation ofN,N'-(1,4-cyclohexylenebismethyl)-bis[2-hydroxydecylamine] and tworecrystallizations of the resulting product from methanol gaveN,N'-cyclohexylenebismethyl-bis[N-methyl-2-hydroxydecylamine] (I: R= CH₃(CH₂)₇, R' = H, X= CH₂ CH(CH₂ CH₂)₂ CHCH₂, Z= H) (8.9 g., m.p. 66°-69°C.).

EXAMPLE 66

In a manner similar to that of Example 1, condensation of 1-dodeceneoxide (50 g.) and 1,4-cyclohexylenebis(methylamine) (19.3 g.) andrecrystallization of the resulting product from methanol gaveN,N'-(1,4-cyclohexylenebismethyl)-bis[2-hydroxydodecylamine] (I: R= CH₃(CH₂)₉, R' = H, X= CH₂ CH(CH₂ CH₂)₂ CHCH₂, Z= H) (9.5 g., m.p.93.0°-96.0° C.).

EXAMPLE 67

Condensation of 1-decene oxide and cyclobutylidenebis(methylamine)affords N,N'-(cyclobutylidenebismethyl)-bis[2-hydroxydecylamine]##STR10##

EXAMPLE 68

Condensation of 1-decene oxide and 1,2-cycloheptylenebis(methylamine)affords N,N'-(1,2-cycloheptylenebismethyl)-bis[2-hydroxydecylamine]##STR11##

EXAMPLE 69

Condensation of 1-decene oxide and1-(aminomethyl)-4-(2-aminoethyl)cyclohexane affordsN,N'-[cyclohexylene-1-methyl-4-(2-ethyl)]-bis[2-hydroxydecylamine] (I:R= CH₃ (CH₂)₇, R' = H, X= CH₂ CH₂ CH(CH₂ CH₂)₂ CHCH₂, Z= H).

EXAMPLE 70

condensation of 1-decene oxide and1-(aminomethyl)-4-(1-aminoethyl)cyclohexane affordsN,N'-[cyclohexylene-1-methyl-4-(1-ethyl)]-bis(2-hydroxydecylamine] (I:R= CH₃ (CH₂)₇, R' = H, X= CH(CH₃)CH(CH₂ CH₂)₂ CHCH₂, Z= H).

EXAMPLE 71

Condensation of 1-decene oxide and1-(aminomethyl)-4-(4-aminobutyl)cyclohexane affordsN,N'-[cyclohexylene-1-methyl-4-(4-butyl)]-bis[2-hydroxydecylamine] (I:R= CH₃ (CH₂)₇, R' = H, X= (CH₂)₄ CH(CH₂ CH₂)₂ CHCH₂, Z= H).

EXAMPLE 72

Condensation of 1-decene oxide and 1,4-phenylenebis(methylamine) affordsN,N'-(1,4-phenylenebismethyl)-bis[2-hydroxydecylamine] (I: R=, CH₃(CH₂)₇, R' H, Z= 1,4-CH₂ C₆ H₄ CH₂, Z= H).

EXAMPLE 73

Condensation of 1-decene oxide and trans-1,4-(2-butenylene)diamineaffords N,N'-[trans-1,4-(2-butenylene)]-bis[2-hydroxydecylamine] (I: R=CH₃ (CH₂)₇, R'= H, X= trans-CH₂ CH=CHCH₂, Z= H).

EXAMPLE 74

Condensation of 1-decene oxide and 1,4-(2-butynylene)-diamine affordsN,N'-[1,4-(2-butynylene)]-bis[2-hydroxydecylamine] (I: R= CH₃ (CH₂)₇, R'= H, X= CH₂ --CH₂, Z= H).

EXAMPLE 75

A mixture ofN,N'-(1,4-cyclohexylenebismethyl)bis[N-methyl-2-hydroxydecylamine] (3.6g.), phenyl isocyanate (1.78 g.), pyridine (seven drops) and benzene (45ml.) was heated under reflux (for 3hr.), then filtered. The filtrate wasdiluted with hexane (10 ml.), and the resulting product (2.4 g.) wasrecrystallized from methanol, affordingN,N'-(1,4-cyclohexylenebismethyl)bis(N-methyl-2-hydroxydecylamine]dicarbanilate (I: R= CH₃ (CH₂)₇, R'= CH₃, X= CH₂ CH(CH₂ CH₂)₂ CHCH₂, Z=CONHC₆ H₅) (m.p. 74°-76° C.).

EXAMPLE 76

Condensation ofN,N'-(1,4-cyclohexylenebismethyl)bis[N-methyl-2-hydroxydecylamine] ando-tolyl isocyanate affordsN,N'-(1,4-cyclohexylenebiasmethyl)-bis-[N-methyl-2-hydroxydecylamine]bis(o-methylcarbanilate) (I: R= Ch₃ (CH₂)₇, R' = CH₃, X = Ch₂ CH(CH₂CH₂)₂ CHCH₂, Z= CONHC₆ H₄ CH₃ -o).

EXAMPLE 77

Condensation ofN,N'-(1,4-cyclohexylenebismethyl)-bis[N-methyl-2-hydroxydecylamine] andp-bromophenyl isocyanate affordsN,N'-(1,4-cyclohexylenebismethyl)-bis[N-methyl-2-hydroxydecylamine]bis(p-bromocarbanilate) (I: R= CH₃ (CH₂)₇, R' = CH₃, X= CH₂ CH(CH₂ CH₂)₂CHCH₂, Z= CONHC₆ H₄ Br-p).

EXAMPLE 78

Condensation ofN,N'-(1,4-cyclohexylenebismethyl)-bis[N-methyl-2-hydroxydecylamine] and4-chloro-o-tolyl isocyanate affordsN,N'-(1,4-cyclohexylenebisamethyl)-bis[N-methyl-2-hydroxydecylamine]bis(2-methyl-4-chlorocarbanilate) (I: R= CH₃ (CH₂)₇, R' = CH₃, X= CH₂CH(CH₂ CH₂)₂ CHCH₂, Z= CONHC₆ H₃ CH₃ -2-Cl-4).

EXAMPLE 79

Condensation ofN,N'-(1,4-cyclohexylenebismethyl)-bis[N-methyl-2-hydroxydecylamine] and5-chloro-2,4-dimethoxyphenyl isocyanate affordsN,N'-(1,4-cyclohexylenebismethyl)-bis[N-methyl-2-hydroxydecylamine]bis(5-chloro-2,4-dimethoxycarbanilate) (I: R= CH₃ (CH₂)₇, R'= CH₃, X=CH₂ CH(CH₂ CH₂)₂ CHCH₂, Z= CONHC₆ H₂ (OCH₃)₂ -2,4-Cl-5).

EXAMPLE 80

Condensation ofN,N'-(1,4-cyclohexylenebismethyl)-bis[N-methyl-2-hydroxydecylamine] andm-(trifluoromethyl)phenyl isocyanate affordsN,N'-(1,4-cyclohexylenebismethyl)bis-[N-methyl-2-hydroxydecylamine]bis(m-(trifluoromethyl)carbanilate] (I: R= CH₃ (CH₂)₇, R' = CH₃, X= CH₂CH(CH₂ CH₂)₂ CHCH₂, Z= CONHC₆ H₄ CF₃ -m).

EXAMPLE 81

Condensation ofN,N'-(1,4-cyclohexylenebismethyl)bis[N-methyl-2-hydroxydecylamine] andp-acetamidophenyl isocyanate affordsN,N'-(1,4-cyclohexylenebismethyl)-bis[N-methyl-2-hydroxydecylamine]bis(p-acetamidocarbanilate) (I: R= CH₃ (CH₂)₇, R' = CH₃, X= CH₂ CH(CH₂CH₂)₂, Z= CONHC₆ H₄ -NHCOCH₃ -p).

EXAMPLE 82

Condensation ofN,N'-(1,4-cyclohexylenebismethyl)bis[N-methyl-2-hydroxydecylamine] andm-nitrophenyl isocyanate affordsN,N'-(1,4-cyclohexylenebismethyl)-bis[N-methyl-2hydroxydecylamine]bis(m-nitrocarbanilate) (I: R= CH₃ (CH₂)₇, R'= CH₃, X= CH₂ CH(CH₂ CH₂)₂CHCH₂, Z= CONHC₆ H₄ NO₂ -m).

EXAMPLE 83

Condensation ofN,N'-(1,4-cyclohexylenebismethyl)-bis[N-methyl-2-hydroxydecylamine] andp-(methylsulfonyl)phenyl isocyanate affordsN,N'-(1,4-cyclohexylenebiamethyl)-bis[N-methyl-2-hydroxydecylamine]bis[p-(methylsulfonyl)carbanilate] (I: R= CH₃ (CH₂)₇, R' = CH₃, X= CH₂CH(CH₂ CH₂ ₂ CHCH₂, Z= CONHC₆ H₄ SO₂ CH₃ -p). ##STR12##

EXAMPLE 84

Hydrogen peroxide (30%, 164 ml.) was added dropwise with stirring to asolution of N,N'-(1,6-hexylene)-bis[N-methyl-2-hydroxyundecylamine](51.6 g.) in alcohol (200 ml.). The temperature was maintained at about25° C. with cooling during the addition. The solution was allowed tostand overnight at room temperature. A small amount ofpalladium-on-carbon was added and the mixture was allowed to standovernight again. The mixture was filtered and the solvents were strippedfrom the filtrate, leaving an oil. Crystals which separated from anacetone solution of the oil were recrystallized from acetone, affordingN,N'-(1,6-hexylene)-bis-[N-methyl-2-hydroxyundecylamine]N,N'-dioxide(IV: R== CH₃ (CH₂)₈, R' = CH₃, X= (CH₂)₆)(3.2 g., m.p. 168.0°-170.6°C.).

Table III shows the results of the antibacterial testing in vitro ofN,N'-(1.6-hexylene)-bis[N-methyl-2-hydroxyundecylamine]N,N'-dioxide.

                  Table III                                                       ______________________________________                                                      Bacteriostatic con-                                                                         Bactericidal con-                                 Microorganism centration (p.p.m.)                                                                         centration (p.p.m.)                               ______________________________________                                        Staphylococcus aureus                                                                       10            25                                                Eberthella typhi                                                                            >100          --                                                Clostridium welchii                                                                         10            10                                                Pseudomonas aeruginosa                                                                      100           >100                                              ______________________________________                                    

EXAMPLE 85

In a manner similar to that of Example 84, oxidation ofN,N'-(1,6-hexylene)-bis[N-methyl-2-hydroxyheptylamine] (20.2 g.) and tworecrystallizations of the resulting product from acetone gaveN,N'-(1,6-hexylene)-bis[N-methyl-2-hydroxyheptylamine] N,N'-dioxide (IV:R= CH₃ (CH₂)₄, R' = CH₃, X= (CH₂)₆) (6.0 g., m.p. 148.0°-152.4° C.).

EXAMPLE 86

In a manner similar to that of Example 84, oxidation ofN,N'-(1,6-hexylene)-bis[N-methyl-2-hydroxyoctylamine] (30.3 g.) andrecrystallization of the resulting product from acetonitrile gaveN,N'-(1,6-hexylene)-bis[N-methyl-2-hydroxyoctylamine] N,N'-dioxide (IV:R= CH₃ (CH₂)₅, R' = CH₃, X= (CH₂)₆) (26.1 g., m.p. 143.8°-145.5° C.).

EXAMPLE 87

In a manner similar to that of Example 84, oxidation ofN,N'-(1,6-hexylene)-bis[N-methyl-2-hydroxynonylamine] andrecrystallization of the resulting product from acetonitrile gaveN,N'-(1,6-hexylene)-bis[N-methyl-2-hydroxynonylamine] N,N'-dioxide (IV:R= CH₃ (CH₂)₆, R' = CH₃, X= (CH₂)₆) (19.3 g., m.p. 155.0°-157.6° C.).

EXAMPLE 88

In a manner similar to that of Example 84, oxidation ofN,N'-(1,6-hexylene)-bis[N-methyl-2-hydroxydecylamine] (31.7 g.) and tworecrystallizations of the resulting product from acetone-methanol gaveN,N'-(1,6-hexylene)-bis[N-methyl-2-hydroxydecylamine] N,N'-dioxide (IV:R= CH₃ (CH₂)₇, R' = CH₃, X= (CH₂)₆) (4.0 g., m.p. 162.0°-166.0° C.).

EXAMPLE 89

In a manner similar to that of Example 84, oxidation ofN,N'-(1,6-hexylene)-bis[N-methyl-2-hydroxydodecylamine] (40 g.) and tworecrystallizations of the resulting product from acetone-methanol gaveN,N'-(1,6-hexylene)-bis[N-methyl-2-hydroxydodecylamine] N,N'-dioxide(IV: R= CH₃ (CH₂)₉, R' = CH₃, X= (CH₂)₆) (10.4 g., m.p. 163.6°-166.0°C.).

EXAMPLE 90

In a manner similar to that of Example 84, oxidation ofN,N'-(1,6-hexylene)-bis[N-methyl-2-hydroxytetradecylamine] (28.2 g.) andtwo recrystallization of the resulting product from acetone-methanolgave N,N'-(1,6-hexylene)-bis[N-methyl-2-hydroxytetradecylamine]N,N'-dioxide (IV: R= CH₃ (CH₂)₁₁, R' = CH₃, X= (CH₂)₆) (8.8 g., m.p.150.0°-155.0° C.).

Examples 91-98 are N,N'-diammonium quaternary salts of the formula##STR13##

EXAMPLE 91

A mixture of N,N'-(1,6-hexylene)-bis[N-methyl-2-hydroxyundecylamine] (10g.), methyl chloride (34 g.) and acetonitrile (30 ml.) was heated in abomb (60°-65° C., 4 hr.). The resulting product (3.6 g.) wasrecrystallized from acetonitrile affordingN,N'-(1,6-hexylene)-bis[N,N-dimethyl-2-hydroxyundecylammonium]dichloride(V: R= CH₃ (CH₂)₈, R' = R" = CH₃, X= (CH₂)₆, Y= Cl) (7.0 g., m.p.171.0°-174.8° C.).

Table IV shows the results of the antibacterial testing in vitro ofN,N'-(1,6-hexylene)-bis[N,N-dimethyl-2-hydroxyundecylammonium]dichloride.

                  Table IV                                                        ______________________________________                                                      Bacteriostatic con-                                                                         Bactericidal con-                                 Microorganism centration (p.p.m.)                                                                         centration (p.p.m.)                               ______________________________________                                        Staphylococcus aureus                                                                       2.5           2.5                                               Eberthella coli                                                                             50            50                                                Pseudomonas aeruginosa                                                                      50            >100                                              Proteus vulgaris                                                                            >100                                                            ______________________________________                                    

EXAMPLE 92

In a manner similar to that of Example 91, quaternerization ofN,N'-(1,6-hexylene)-bis[N-methyl-2-hydroxydecylamine](two runs, 10 g.each) with methyl chloride (40 ml. one run, 28 g. other run) andrecrystallization of the combined products from acetonitrile gaveN,N'-(1,6-hexylene)-bis[N,N-dimethyl-2-hydroxydecylammonium]dichloride(V: R= CH₃ (CH₂)₇, R' = R" = CH₃, X= (CH₂)₆, Y= Cl) (18.7 g., m.p.171.0°-174.0° C.).

EXAMPLE 93

Quaternerization of N,N'-(1,6-hexylene)-bis[N-methyl2-hydroxydecylamine]with methyl iodide affordsN,N'-(1,6-hexylene)-bis[N,N-dimethyl-2-hydroxydecylammonium]dichloride(V: R= CH₃ (CH₂)₇, R' = R" = CH₃, X= (CH₂)₆, Y= I).

EXAMPLE 94

Quaternerization of N,N'-(1,6-hexylene)-bis[N-methyl2-hydroxydecylamine]with ethyl p-toluenesulfonate affordsN,N'-(1,6-hexylene)-bis[N-ethyl-N-methyl-2-hydroxydecylammonium]bis(p-toluenesulfonate (V: R= CH₃ (CH₂)₇, R' = CH₃, R" = CH₃ CH₂, X=(CH₂)₆, Y= SO₃ C₆ H₄ CH₃ -P).

EXAMPLE 95

Quaternerization ofN,N'-(1,6-hexylene)-bis[N-methyl-N-propyl-2-hydroxydecylamine] withpropyl bromide affordsN,N'-(1,6-hexylene)-bis(N-methyl-N-propyl-2-hydroxydecylamonium]dibromide (V: R= CH₃ (CH₂)₇, R' = CH₃, R" = CH₃ (CH₂)₂, X= (CH₂)₆, Y=Br).

EXAMPLE 96

Quaternerization of N,N'-(1,6-hexylene)-bis[N-methyl2-hydroxydecylamine]with isobutyl iodide affordsN,N'-(1,6-hexylene)-bis[N-isobutyl-n-methyl-2-hydroxydecylammonium]diiodide (V: R= CH₃ (CH₂)₇, R' = CH₃, R"= (CH₃)₂ CHCH₂, X== (CH₂)₆, Y=I).

EXAMPLE 97

In a manner similar to that of Example 91, quaternerization ofN,N'-(1,6-hexylene)-bis[N-methyl-2-hydroxydodecylamine] (10 g.) withmethyl chloride (34 g.) and recrystallization of the resulting productfrom acetonitrile gaveN,N'-(1,6-hexylene)bis[N,N-dimethyl-2-hydroxydodecylammonium]dichloride(V: R= CH₃ (CH₂)₉, R' = R" = CH₃, X= (CH₂)₆, Y= Cl)(8.5 g., m.p.176.6°-180.0° C.).

Example 98

A mixture of N,N'-(1,6-hexylene)-bis[N-methyl-2-hydroxyheptylamine] (5g.), benzyl bromide (4.7 g.) and hexane (60 ml.) was heated under reflux(for 5 hr.). Acetonitrile (20 ml.) was added and refluxing was continued(for 5 hr.). the solvents, were stripped and the residue wasrecrystallized from ethylene dichloride, affordingN,N'-(1,6-hexylene)-bis[N-benzyl-N-methyl-2-hydroxyheptylammonium]dibromide (V: R = CH₃ (CH₂)₄, R' = CH₃, R" = C₆ H₅ CH₂, X = (CH₂)₆, Y =Br) (3.5 g., m.p. 127.0°-129.0° C.)

We claim:
 1. N,N'-(X)-bis of the formula ##STR14## wherein: R is alkylof three to fifteen carbon atoms or cycloalkyl of four to seven ringcarbon atoms;R' is hydrogen or atertiary alkyl of one to four carbonatoms; X is X'-Y-X", wherein X' and X" are alkylene of one to fourcarbon atoms with bonds to Y and to the nitrogen atoms at the same ordifferent carbon atoms and Y is cycloslkylene of four to seven ringcarbon atoms with bonds to X' and X" at the same or different carbonatoms;the sum of the number of carbon atoms of R and X is at least nine;Z is hydrogen; or an acid-addition salt thereof; or when R' is atertiaryalkyl of one to four carbon atoms, an N,N'-dioxide thereof. 2.N,N'-(X)-bis wherein:R is alkyl of three to fifteen carbon atoms; R' ishydrogen or atertiary alkyl of one to four carbon atoms; X is X'-Y-X",wherein X' and X" are alkylene of one to four carbon atoms with bonds toY and to the nitrogen atoms at the same or different carbon atoms and Yis cycloalkylene of four to seven ring carbon atoms with the bonds to X'and X" at the same or different carbon atoms; Z is nydrogen; or anacid-addition salt thereof according to claim
 1. 3.N,N'-(x)-bis[N-(R')-2-(R)-2-(ZO)-ethylamine] wherein:R is alkyl of threeto fifteen carbon atoms; R' is hydrogen; X is1,4-cyclohexylenebismethyl; Z is hydrogen; or an acid-addition saltthereof according to claim
 2. 4.N,N'-(1,4-cyclohexylenebismethyl)-bis[2-hydroxyoctylamine] according toclaim
 3. 5. N,N'-(1,4-cyclohexylenebismethyl)-bis[2-hydroxydecylamine]according to claim
 3. 6.N,N'-(cis-1,4-cyclohexylenebismethyl)-bis[2-hydroxydecylamine] accordingto claim
 3. 7.N,N'-(trans-1,4-cyclohexylenebismethyl)-bis[2-hydroxydecylamine]according to claim
 3. 8.N,N'-(1,4-cyclohexylenebismethyl)-bis[2-hydroxydodecylamine] accordingto claim
 3. 9. N,N'-(X)-bis[N-(R')-2-(R)-2-(ZO)-ethylamine] wherein:R isalkyl of three to fifteen carbon atoms; R' is methyl; X is1,4-cyclohexylenebismethyl; Z is hydrogen; or an acid-addition saltthereof according to claim
 2. 10.N,N'-(1,4-cyclohexylenebismethyl)-bis[N-methyl-2-hydroxydecylamine]according to claim 9.